This invention relates to perfluoroalkyl-substituted mono-, di- and poly-amides derived from a perfluoroalkyl iodide, an unsaturated acid and a mono-, di-or polyamine. More particularly it relates to novel compounds which are the reaction products of a mono-, di- or polyamine of 60 to 2000 molecular weight with a perfluoroalkyl-substituted unsaturated acid or its corresponding lower alkyl ester and optionally a non-fluorinated amino-reactive compound such as an acid, ester, anhydride, epichlorohydrin, isocyanate or urea. These RF-amides are useful as internally or externally applied paper sizes to impart oil and grease resistance to paper, and as oil proofing coatings on textiles, wood, masonry and the like, or as high-performance surface active agents.
The use of perfluoroalkyl-substituted polymers to impart oil and water repellency to a variety of substrates, textiles especially, has long been known. The vast majority of these polymers are perfluoroalkyl-substituted methacrylate copolymers. Several patents also describe RF-substituted polyurethanes, where RF stands for a perfluoroalkyl moiety. Polyamide-amino polymers derived from polyethyleneimine by reaction with esters of perfluoroalkyl-substituted carboxylic acids are described in U.S. Pat. Nos. 3,769,307 and 3,567,500. These polymers contain a mixture of RF-substituted amide and secondary amino groups. These polymers are used to impart oleophobicity yet hydrophlilicity to textile substrates. Di-RF amido monocarboxylic acids prepared from 1 equivalent of diethylenetriamine, 2 equivalents of an RF-acid and 1 equivalent of an anhydride are taught for use as textile finishes in U.S. Pat. No. 3,754,026. Similar RF-amide-substituted polyethyleneimines useful as chemically resistant surfactants are described in U.S. Pat. No. 3,271,430. They are obtained by reaction of a perfluorinated alkanoic acid with a large excess of ethyleneimine. Reaction products of RF-substituted acids with polymers bearing pendent primary amino groups attached to a carbon-carbon backbone by a linking group are claimed in U.S. Pat. No. 4,606,973 as low surface energy coatings on flat substrates.
U.S. Pat. No. 5,643,864 describes the synthesis of anionic surfactants by reaction of, for example, triethylenetetramine with first, two equivalents of a long-chain carboxylic acid, and secondly with chloroacetic acid. RF-substituted acids are claimed as reactants but not described.
U.S. Pat. No. 5,750,043 and U.S. patent application Ser. No. 09/234,251 now U.S. Pat. No. 6,156,222 describe water-soluble RF-substituted carboxylic acids that are amides of polyamines of 100 to 100,000 molecular weight which are used as foam stabilizers for aqueous fire fighting foams
It has now been discovered that unsaturated alkenoic acids, preferably xcfx89perfluoroalkyl substituted 10-undecenoic acid and tetrahydrophthalic acid, can be converted by reaction with a large variety of amines into mono-, di- and polyamides, which can be further reacted with non-fluorinated amino-reactive compounds such as acids, acid chlorides, esters, anhydrides, epichlorohydrin, isocyanates or urea to form monomeric and polymeric amides, amino-ethers, and ureas which are uniquely suitablexe2x80x94depending on their specific structurexe2x80x94as specialty surfactants or as oil and water repellents when applied to paper, textiles, wood, glass or masonry.
Perfluoroalkyl substituents which are attached to a long-chain hydrocarbon moiety, such as an undecenoic group, exhibit improved surface activity and improved effectiveness as oil repellents, possibly because such long-chain hydrocarbyl groups, by their inter-chain interactions, aid in the orientation of the very poorly interacting RF-groups.
xcfx89-Perfluoroalkyl-substituted 10-undecenoic acid and its use as an oil repellent paper size is disclosed in U.S. Pat. No. 5,491,261. Due to its relatively low molecular weight, this compound however shows substantial weight loss at the temperatures required for many paper product applications. This shortcoming has been overcome with the amide compounds of the present invention, which incorporate hydrogen-bonding amide groups and preferably contain more than one perfluoroalkyl-substituted undecenoic group.
The compounds of the present invention are mono-, di- or polyamides of the formulae
(Q)zxe2x80x94Axe2x80x94NHC(xe2x95x90O)xe2x80x94(Wxe2x80x94RF)xxe2x80x83xe2x80x83(I) or 
Axe2x80x94(Q1xe2x80x94Axe2x80x94NHC(xe2x95x90O)xe2x80x94(Wxe2x80x94RF)x)yxe2x80x94NHC(xe2x95x90O)xe2x80x94(Wxe2x80x94RF)xxe2x80x83xe2x80x83(II), 
wherein
A is the hydrocarbon residue of an aliphatic, cycloaliphatic or aromatic mono-, di- or polyamine of 60 to 2000 molecular weight, which is optionally substituted by hydroxy- and/or carboxyl groups and whose carbon chain is optionally interrupted by one or more ether, amide or amino groups, which amino groups are optionally substituted by substituents of the formula xe2x80x94Qxe2x80x94 or xe2x80x94Q1xe2x80x94, in which
Q is a monovalent radical connected to a nitrogen atom of (A) and is derived from an acid, acid chloride or lower alkyl ester, an anhydride, a halogenated carboxylic acids an alkyl or alkenyl halide, an oxirane compound or chloroacetamide, and which is optionally substituted by one or more hydroxy-, tert. amino or carboxyl groups, or is optionally interrupted by one or more ether or thioether linkages, and optionally contains one or more unsaturated groups and can be substituted by an RF group, or is xe2x80x94P(xe2x95x90O)(OH)2; xe2x80x94SO3H; or xe2x80x94C(xe2x95x90O)xe2x80x94NH2;
Q1 is a difunctional linking group attached to the nitrogen atoms of two A groups and is derived from a diacid, diacid chloride or -lower alkyl ester, a dianhydride, a diisocyanate, epichlorohydrin, or is xe2x80x94C(xe2x95x90O)xe2x80x94, or is a trifunctional group derived from cyanuric acid,
each RF is independently a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
W is xe2x80x94(CH2)pCHxe2x95x90CHxe2x80x94 in which p is 1 to 20, or is a C6-C10cycloaliphatic hydrocarbyl group connecting an RF group to an amide carbonyl,
z is zero to 50,
y is zero to 50 and
x is 1 to 10.
The compounds of the present invention preferably have a number average molecular weight of 1,000 to 10,000.
Preferably W is of the formula xe2x80x94(CH2)pCHxe2x95x90CHxe2x80x94 in which p is 5 to 12 and is derived from a terminally unsaturated alkenoic acid, or is derived from tetrahydrophthalic anhydride or (methyl)-norbornene anhydride; RF is saturated and contains 4-14 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group.
Most preferably W is of the formula xe2x80x94(CH2)pCHxe2x95x90CHxe2x80x94 in which p is 8, and RF is saturated and contains 6-12 fully fluorinated carbon atoms.
When A is the hydrocarbon residue of an optionally substituted and/or interrupted monoamine, the amine is preferably an amino acid such as glycine, p-aminosulfonic acid or taurine, or an amino alcohol such as 2-hydroxyethanolamine or is a tert. amino-substituted amine residue of the formula xe2x80x94(CH2)jxe2x80x94Nxe2x80x94(R1)2 wherein j is 2 to 6 and each R1 is independently C1-C4alkyl, such as N,N-dimethylpropane-1,3-diamine. Especially preferred is a compound of the formula (II) wherein A is a tert. amino-substituted amine residue of the formula xe2x80x94(CH2)jxe2x80x94Nxe2x80x94(R1)2 wherein j is 2 to 6 and each R1 is independently C1-C4alkyl, W is of the formula xe2x80x94(CH2)pCHxe2x95x90CHxe2x80x94 in which p is 8, and RF is saturated and contains 6-12 fully fluorinated carbon atoms.
When A is the hydrocarbon residue of an optionally substituted and/or interrupted diamine, the diamine is preferably of the formula H2Nxe2x80x94(CH2)nxe2x80x94NH2 wherein n is 2-6, or is p-phenylenediamine, lysine, or a diamine of the formula
H2Nxe2x80x94(CH2)3xe2x80x94Oxe2x80x94(CH2xe2x80x94CH2xe2x80x94O)mxe2x80x94(CH2xe2x80x94CHCH3xe2x80x94O)lxe2x80x94(CH2)3xe2x80x94NH2, wherein m and l are independently 0 to 50 and m plus l is xe2x89xa71.
When A is the hydrocarbon residue of an optionally substituted and/or interrupted polyamine, the amine is preferably a polyalkyleneamine of the formula
H2Nxe2x80x94(CH2CHRxe2x80x94NH)nxe2x80x94CH2CHRxe2x80x94NH2, wherein n is 1 to 5 and R is hydrogen or methyl, or is aminoethylpiperazine, iminobispropylamine or N,Nxe2x80x2-bis(3-aminopropyl)ethylenediamine, or is a polyethyleneimine of molecular weight 200 to 2,000 or polylysine.
Most preferably A is derived from a polyethyleneimine of molecular weight 200 to 1,000, diethylenetriamine, triethylenetetramine, N,Nxe2x80x2-bis(3-aminopropyl)ethylenediamine, lysine or polylysine.
Preferred Q are of formula xe2x80x94C(xe2x95x90O)CH3; xe2x80x94(CH2)1-3COOH; xe2x80x94C(xe2x95x90O)xe2x80x94CRxe2x95x90CH2, wherein R is hydrogen or methyl; xe2x80x94CH2CHxe2x95x90CH2; xe2x80x94CH2CH(OH)CH2xe2x80x94Oxe2x80x94CH2CHxe2x95x90CH2; xe2x80x94CH2CHxe2x95x90CHxe2x80x94RF or xe2x80x94CH2CH(OH)CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94RF, where RF is defined as above; xe2x80x94C(xe2x95x90O)xe2x80x94(CH2)2xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94CHxe2x95x90CHxe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94C(xe2x95x90CH2)xe2x80x94CH2xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94CH2xe2x80x94C(xe2x95x90CH2xe2x80x94COOH; xe2x80x94C(xe2x95x90O)(C6H8)xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94(C7H8)xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94(C8H10)xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94(CH2)8CHxe2x95x90CH2; xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94Oxe2x80x94(CH2CHRxe2x80x94O)mxe2x80x94R2 where m is 1 to 50 and R2 is hydrogen or C1-C12alkyl; xe2x80x94P(xe2x95x90O)(OH)2; xe2x80x94SO3H; or xe2x80x94CH2CH2N(CH3)2.
Most preferred are Q of formulae xe2x80x94C(xe2x95x90O)CH3; xe2x80x94C(xe2x95x90O)xe2x80x94CHxe2x95x90CH2; xe2x80x94CH2xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94(CH2)2xe2x80x94COOH and xe2x80x94C(xe2x95x90O)xe2x80x94(C6H8)xe2x80x94COOH.
Preferred Q1 are of formula xe2x80x94(Cxe2x95x90O)xe2x80x94HNxe2x80x94Zxe2x80x94NHC(xe2x95x90O)xe2x80x94, wherein Z is the diradical hydrocarbon residue of p- or m-toluene diisocyanate, isophorone diisocyanate, 3,3,4(3,4,4)-trimethylhexane-1,6-diisocyanate or hexane-1,6-diisocyanate; xe2x80x94C(xe2x95x90O)xe2x80x94; xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94 or xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94Oxe2x80x94(CH2CH2xe2x80x94O)mxe2x80x94(CH2CHCH3xe2x80x94O)lxe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94, wherein m and l are independently 0 to 50 and m plus l is xe2x89xa71 ;xe2x80x94C(xe2x95x90O)xe2x80x94C6H4(xe2x80x94COOH)2xe2x80x94C(xe2x95x90O)xe2x80x94; or xe2x80x94C(xe2x95x90O)xe2x80x94CH2C(xe2x95x90CH2)xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94C(xe2x95x90O)xe2x80x94Dxe2x80x94C(xe2x95x90O)xe2x80x94, wherein D is the hydrocarbon residue of an aliphatic or aromatic dicarboxylic acid having from 2 to 10 carbon atoms.
Most preferred Q1 are of formula xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94C6H4(xe2x80x94COOH )2xe2x80x94C(xe2x95x90O)xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94CH2CH2xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94C(xe2x95x90O)HNxe2x80x94Zxe2x80x94NHC(xe2x95x90O)xe2x80x94 wherein Z is the diradical residue of p- or m-toluene diisocyanate, isophorone diisocyanate, 3,3,4(3,4,4)-trimethylhexane-1,6-diisocyanate or hexane-1,6-diisocyanate.
The most preferred compounds of the formula (I) are of the formula
Qzxe2x80x94Axe2x80x94(C(xe2x95x90O)xe2x80x94(CH2)8CHxe2x95x90CHxe2x80x94RF)2xe2x80x83xe2x80x83(III), 
wherein
A is derived from diethylenetriamine, triethylenetetramine or N,Nxe2x80x2-bis(3-aminopropyl)ethylene-diamine, Q is xe2x80x94C(xe2x95x90O)CH3; xe2x80x94C(xe2x95x90O)xe2x80x94CHxe2x95x90CH2; xe2x80x94CH2xe2x80x94COOH; xe2x80x94C(xe2x95x90O)xe2x80x94(CH2)2xe2x80x94COOH or xe2x80x94C(xe2x95x90O)xe2x80x94(C6H8)xe2x80x94COOH, z is 1 or 2, and each RF is independently a monovalent perfluorinated linear alkyl radical having 6 to 14 fully fluorinated carbon atoms.
Most preferred compounds of the formula (II) are of formula
(Q1xe2x80x94Axe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94(CH2)8CHxe2x95x90CHxe2x80x94RF)2xe2x80x94Axe2x80x94(NHxe2x80x94C(xe2x95x90O)xe2x80x94(CH2)8CHxe2x95x90CHxe2x80x94RF)2xe2x80x83xe2x80x83(IV), 
wherein A is derived from diethylenetriamine and Q1 is a difunctional radical of the formula xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94CH2CH2xe2x80x94C(xe2x95x90O)xe2x80x94; xe2x80x94C(xe2x95x90O) xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94C6H4(xe2x80x94COOH)2xe2x80x94C(xe2x95x90O)xe2x80x94, or xe2x80x94C(xe2x95x90O)xe2x80x94NHxe2x80x94Zxe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94, wherein Z is the diradical hydrocarbon residue of p- or m-toluene diisocyanate, isophorone diisocyanate, 3,3,4(3,4,4)-trimethylhexane-1,6-diisocyanate or hexane-1,6-diisocyanate and each RF is independently a monovalent perfluorinated linear alkyl radical having 6 to 14 fully fluorinated carbon atoms; most particularly a dimeric compound of the formula
(RFxe2x80x94CHxe2x95x90CH(CH2)8C(xe2x95x90O)xe2x80x94NH)2xe2x80x94Axe2x80x94Q1xe2x80x94Axe2x80x94(NHC(xe2x95x90O)(CH2)8CHxe2x95x90CHxe2x80x94RF)2xe2x80x83xe2x80x83(V), 
wherein RF, A and Q1 are as defined above.
Also most preferred compounds of the formula (II) are of the formula
Axe2x80x94(Q1xe2x80x94Axe2x80x94(NHC(xe2x95x90O)(CH2)8CHxe2x95x90CHxe2x80x94RF)2)yxe2x80x94(NHC(xe2x95x90O)(CH2)8CHxe2x95x90CHxe2x80x94RF)2xe2x80x83xe2x80x83(VI), 
wherein
y is 2 to 50, A is derived from triethylenetetramine or Nxe2x80x2N-bis(3-aminopropyl)ethylenediamine and difunctional Q1 is of the formula CH2xe2x80x94CHOHxe2x80x94CH2xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94CH2CH2xe2x80x94C(xe2x95x90O)xe2x80x94; xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)xe2x80x94C6H4(xe2x80x94COOH)2xe2x80x94C(xe2x95x90O)xe2x80x94, or xe2x80x94C(xe2x95x90O)xe2x80x94HNxe2x80x94Zxe2x80x94NHxe2x80x94C(xe2x95x90O)xe2x80x94, wherein Z is the diradical hydrocarbon residue of p- or m-toluene diisocyanate, isophorone diisocyanate, 3,3,4(3,4,4)-trimethylhexane-1,6-diisocyanate or hexane-1,6-diisocyanate, thus describing polymers of formula
(RFxe2x80x94CHxe2x95x90CH(CH2)8(Cxe2x95x90O)HN)2xe2x80x94Axe2x80x94(Q1xe2x80x94Axe2x80x94(NHC(xe2x95x90O)(CH2)8CHxe2x95x90CHxe2x80x94RF)2)yxe2x80x83xe2x80x83(VII) 
which are polyamides, polyureas or poly-tert. amines.
The novel RF-products of the formula (I) or (II) can be synthesized in various ways. In one method, an aliphatic, cycloaliphatic or aromatic mono-, di- or polyamine is in a first step reacted with an RF-acid, -ester or -anhydride at temperatures of 50 to 260xc2x0 C., depending on the reactivity of the acid or ester, to form the corresponding RF-amide intermediate which may contain unreacted secondary amino groups.
This amidification reaction is preferably carried out in bulk, but aprotic diluents can be present. Preferably a catalyst such as phosphoric acid is employed.
In a second step any remainingxe2x80x94mostly secondaryxe2x80x94amino groups are reacted with an amino-reactive non-fluorinated compound. Useful reactants to convert remaining unreacted amino groups include anhydrides such as acetic anhydride, succinic and maleic anhydride, methendic and phthalic or tetrahydrophthalic anhydride; C1-C8carboxylic acids and their methyl esters; chloroacetic acid; alkyl halides such as allyl chloride; allyl glycidyl ether, urea and isocyanates.
If the reactants are difunctional reactants they can act as chain-extending agents. Typical of such compounds are diacids and their lower alkyl esters, such as glutaric acid and dimethylsuccinate or dimethyladipate, or anhydrides such as succinic and maleic anhydride, methendic and phthalic anhydride, also dianhydrides such as benzene- and benzophenone tetracarboxylic acid dianhydride; epichlorohydrin; urea, and aliphatic, cycloaliphatic and aromatic diisocyanates with 6 to 2 carbon atoms, such as 1,6-hexane diisocyanate, 2,2,3(2,3,3)-trimethylhexane-1,6-diisocyante, cyclohexane diisocyanate, isophorone diisocyanate and toluene diisocyanate. If the starting polyamine (P) is for example N,Nxe2x80x2-bis-(3-aminopropyl) ethylenediamine, or a polyethyleneimine, the resulting reaction products are polyureas and polyamides.
In an alternate process, which is especially useful to prepare the most preferred compositions of this invention, a linear terminally-unsaturated monocarboxylic acid or its lower alkyl ester, or tetrahydrophthalic anhydride is first reacted with a polyamine, to form an oligoamide with residual secondary amino groups. Preferably this reaction is carried out without a solvent. Although, it is possible to use other linear terminally-unsaturated monocarboxylic acids, 10-undecenoic acid or its lower alkyl ester is preferred because RF substituents which are attached to the amino group through an intervening undecenoic group aid in the orientation of the RF groups and thereby improve their effectiveness as oil repellents.
In a second step, the remaining secondary amino groups are reacted with an amino-reactive non-fluorinated compound of the type described above to form a fully substituted intermediate. Finally, this ethylenically unsaturated intermediate is reacted with an RF-iodide using a free radical generating mechanism as described for instance in U.S. Pat. Nos. 5,585,517 and 5,693,747; and in copending U.S. patent application Ser. No. 09/691,486.
Substituents xe2x80x94CH2CHxe2x95x90CHxe2x80x94RF or xe2x80x94CH2CH(OH)CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94RF, where RF is defined as above can be incorporated into the compound by reaction of amino groups with allyl chloride or allyl glycidyl ether at any convenient stage during the synthesis, but before the addition of the RF-iodide.
Halogen-containing compounds, such as allyl chloride, mono-chloroacetic acid, chloromethyl benzene, xylylene dichloride, or methyl iodide or bromide can be further used for quaternization of tertiary amino groups. Tertiary amino groups are always present in polyethyleneimines, and also if allyl chloride or allyl glycidyl ether are used as co-reactants.
The final product mixture is then diluted, if desired, with sufficient deionized water to adjust the solids content to 15 to 50% and the fluorine content to 4 to 10%. Thus another aspect of the present invention is an essentially aqueous solution comprising 15 to 50% of a compound of the formula (I) or (II) as defined above.
The compounds of the formula (I) or (II) as defined above are useful as internally or externally applied paper sizes to impart oil and grease resistance to paper, and oil and grease resistant coatings on textiles, wood, masonry and the like, or as high-performance surface active agents.
When the compounds of the present invention are used as grease and oil repellent paper sizing agents, they are applied by methods known per se in amounts that are sufficient to deposit from 0.005 to 0.5% of organically bound fluorine by weight based on the dry paper weight. The compounds of the present invention can be applied externally in topical applications, for instance in a size press to the surface of paper or cardboard. They can also be applied internally, by adding them to an aqueous pulp together with other wet-end chemicals, as described for instance in U.S. Pat. No. 5,091,550, the disclosure of which is incorporated by reference, and more generally in W. F. Reynolds, xe2x80x9cThe Sizing of Paperxe2x80x9d, TAPPI Press, 1989. The compounds of the present invention are especially useful to impart oil and grease resistance to paper that is used for food packaging or contact applications.
Thus another aspect of the present invention is a method to impart oil and grease resistance to paper, which comprises incorporating an amount of a compound of the formula (I) or (II) as defined above that is effective to impart oil and grease resistance into the paper. Advantageously this method comprises treating paper or pulp with essentially aqueous solution comprising a sufficient amount of a compound of the formula (I) or (II) as defined above to deposit from 0.005 to 0.5% of organically bound fluorine by weight based on the dry weight of the paper onto the paper or pulp.
In addition to the fluorochemical, any of the conventional binders used in the paper industryxe2x80x94such as polymeric latex binders, carboxymethyl cellulose and polyvinyl alcoholxe2x80x94and sizing agents, such as ionic and nonionic starches such as ethoxylated and oxidized starches, and water sizing agents such as alkyl ketene dimer (AKD) or alkylsuccinic anhydride (ASA) can be employed.
The present invention further relates to a method to impart oil and grease resistance to a textile material, which comprises treating the textile material with an amount of a compound of the formula (I) or (II) as defined above that is effective to impart oil and grease resistance to the textile material.
The preferred amounts of the compounds of the present invention to treat the textile material are the same as for paper or pulp.
The present invention further relates to textile material or paper or pulp which contains from 0.005 to 0.5% by weight of a compound of the present invention incorporated therein.
The following examples describe certain embodiments of this invention, but the invention is not limited thereto. It should be understood that numerous changes to the disclosed embodiments could be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. These examples are therefore not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. In these examples all parts given are by weight unless otherwise indicated.
Unless otherwise noted, in the following non-limiting examples the perfluoroalkyl iodide (RFI) used is Zonyl Tel A-N from DuPont, with a homologue distribution of 53.0% C8F17I, 30.6% C10F21I, 11.7% C12F25I, 3.6% C14F29I, and 1.0% C16F33I.
Examples 1-10 describe the synthesis of di- and tri-RF substituted N,Nxe2x80x2-bis(3-aminopropyl)-ethylenediamine (APEDA) reaction products of the formula 